Method and apparatus for preparing mixed sulfur-hydrocarbon vapors



J1me 1951 M. M; MARISIC ETAL 2,556,430

METHOD AND APPARATUS FOR PREPARING MIXED SULFUR-HYDROCARBON VAPORS 3 Sheets-Sheet 1 Filed April 21, 1945 I a w m 6 7 0V m w 8 z z a a q u w E a w J "n" n .nHHm n n u u u 7 u w I 5 a F ma mr Q a p am a 8 K 2 5 HOP GI' INVENTORS W2 i 'l o BY 5W ATTORNEY June 12, 1951 v M. M. MARISIC ETAL AND APP I METHOD Filed April 21, 1945 3 Sheets-Sheet 2 v I W 6; mm M v m W0 e H+ m\ o E a w J w e 5 I l v 4. r v v m. \u u a w n M 6 6 1? "I aw 4 m M w 2 4. 6. H 0 DE P6 M1 M M, M 5 2 "M 2. 1 J 4 4 0u 1 r\. M n. l.b.| uu r 5 0 4 0 nHu nuu e f 45 5. 4 HHWU w w a mmmmw H g m; W H

rw in mm .INVENTORS axles .11. mLfionM ATTORNEY Patented June 12 1 assent UNITED STATES ll-PATENT GFPEQE METHOD AND APPARATUS FOR PREPARING MIXED SULFUR HYDR'OUARBON VAPORS Milton M. Marisic, Northfield, and Charles A. Porter, Chicago, Ill.,'assignors to The Pure Oil Company, Chicago, Ill.,-.a corporation of Ohio Application-April 21, 1945, SerialNo. 589,680

14' Claims.

. 1 This invention relates-toe method and apparatus for preparing -a-mixtureof sulfur vapors and gaseous or vaporoushydrocarbons.

In various-known processes itis-necessary to react sulfur at hightemperatures with hydrometals and alloys at high temperatures.

An object of this invention is to provide method and apparatus-for vaporizing and superheating sulfur vapors.

Another object of this invention is to provide method and apparatus for preparing amixture of vaporized sulfur and gaseous'or vaporous hydrocarbons for subsequent reaction with each other.

A still further object of the invention is to provide method and apparatus for vaporizing and superheating sulfur vapors in a manner to eliminate corrosion difficulties encountered when vaporization and superheating is conducted ina metallic heating apparatus.

Other objects of theinventionwill become apparent from the description and the accompanying drawings of which:

Figure l is a diagrammatic,elevational view of a form of apparatus for carrying out .our invention;

Figure 2 is a diagrammatic,'elevational view of another form of apparatus for carrying out our invention; and

Figure 3 is a diagrammatic, 'elevational view of-still another form of apparatus forcarrying out our invention.

Referring to Figure 1, numeral l indicates hopper from which finely divided sulfur is fed through line- 2 and Valve 3' to screw conveyor 3 methane or o her gas which it is desired to react with sulfur, is charged throughline-e and-is preheated in furnace l to a temperature approicirnating the melting point of sulfur and then injected into chamber 5 at the end of the screw conveyor Q in order to estate the sulfur and "force it through line 3 to a suitable distributors into vaporizing and:superheating'chamber l0. The

' located in chamber 5. Hydrocarbon gas such as temperature to which the'rnethane or hydrocarbon gas is heated and the quantity of sulfur and methane-are'such that the temperature of the sulfur-gas mixture forced into chamber I0 is approximately 230. F., and in no event as high as the melting point of sulfur. In chamber i0 thefaerated-sulfur contacts a downwardlymov- 7 ing bed of hot refractorynmaterial in granular,

fragmentary or pelleted form. The refractory material may be Carborundum, Alundum, quartz,

fire brick or any other refractorylmaterial which is substantiallyvinert to sulfur at the highv temperatures attained in chamber l6. Upon contactwith the hot refractory material the sulfur is rapidly. melted .and vaporized and theisulfur vapors pass upwardly in counter-current contact with the downwardly moving Need of refractory 'material. Any impurities, such as organic matter orrmineral substances, contained in the sulfur are deposited on the refractory fmaterial and thus removed from the sulfur vapors. During its'passage through chamber It, the'sulfur-gas mixture is superheated to thedesired temperature. Thelsuperheated sulfur vapors andhydrocarbon leave the chamber Hi through line i l and may be charged to a suitable reactor lined with refractory'rnaterial resistant to corrosion for reacting the sulfur and "hydrocarbon. For example; the vapors leaving line I I may be charged directly to a refractory-lined reactor filled wit granular or pelleted silica gel, activated alumina or natural or synthetic alumina-silica catalyst heatedlto a temperature of approximately 1150 to 1200 F. in order to convert the mixture of sulfur vapor and methane or other hydrocarbon to carbon disulfide.

Sufiicientmethane or other hydrocarbon gas preferably similar to that introduced through line 8 is introduced through line E2 and heated in furnace l to a temperature of approximately 900-950 after which it is forced through valve i3 and distributor as into the bottom of chamber it to purge any remaining sulfur from the refractory material prior to its leaving chamber iii. The gas introduced through distributor i l also serves as a sealing medium to prevent sulfur vapor from escaping from the bottom of reactor it. Granular material at a temperature of approximately 990 E. may be withdrawn continuously or intermittently from the bottom of chamher it? through line to controlled by valve it into hopper or receiver ii. A portion of the gas introduced through distributor M will pass into receiver H with the refractory material. This gas is removed from receiver I! through valvecontrolled line [8. The gas withdrawn through line l8 may be recycled to line 12 and fed back into the bottom of the reactor.

The refractory material may be continuously or intermittently withdrawn from receiver ll through line !9 controlled by valve 20 and fed by elevator 2! through line 22 to the top of kiln 23. The refractory material moves downwardly through kiln 23 as a bed and is heated therein by a mixture of combustible gas, liquid, or powdered fuel, and air is introduced through valve-controlled lines 24 and 25. As combustible material, any type of natural gas, artificial gas, such as producer gas, or furnace oils, acid sludges, tars, etc. may be used. The products of combustion are withdrawn from the kiln through valve-controlled lines 26, 2'! and 28. A portion or all of the combustion gases may be circulated through the elevator 2i to preheat the refractory material prior to its entrance into the kiln 23. The valvecontrolled line 28' is provided at the top of the elevator for withdrawing combustion gases circulated through the elevator 2! or which escape from the kiln through line 22.

A portion of the heat in the kiln may be supplied by'burning organic matter deposited on the refractory material during the vaporization of the sulfur. Sulfur generally contains both organic and inorganic impurities which deposit on the refractory material during vaporization.

Sufficient heat is supplied to the kiln 23 to heat the refractory material to a temperature somewhat above the temperature to which it is desired to heat the sulfur vapors. For example, if it is desired to heat the sulfur Vapors to 1200 F., the refractory material may be heated to approximately 1400 F.

Hot refractory material leaves the bottom of the kiln 23 through line 29 and passes through valve 36 into the upper portion of the heating and vaporizing chamber I0. Valve-controlled line 3| is provided in the line 29 above valve 32 for purging flue gases from the refractory material and for sealing chamber against leakage. For this purpose a gas preferably corresponding to that charged to the chamber l0 through line 6 is used and this gas is superheated to at least a temperature which approximates that of the refractory material leaving the bottom of the kiln. The gas is injected into line 29 at a pressure slightly above that existing in chamber in. For example, if the pressure in chamber l6 were 50 pounds per square inch, the pressure of the methane or other gas charged through line 3| would be approximately 52-55 pounds per square inch. A portion of the gas charged to line passes into the kiln 23 where it will be burned and thus will supply a portion of the heat required for heating the refractory material. Another portion of the gas charged through line 31! will pass with the refractory material into chamber if! and become mixed with the sulfur vapors leaving the chamber Ill through line H. Care should be exercised that the total amount of hydrocarbon charged to chamber I5 through lines 6, l2 and 3| does not exceed the amount which it is desired to mix with the sulfur for the subsequent reaction.

The temperature of the refractory material leaving the bottom of chamber it should be above the temperature at which sulfur vaporizes and preferably at a temperature around 909-950" F. The temperature of the refractory material leaving the bottom of the chamber can be controlled by regulation of the temperature of the 4 refractory material entering chamber l0, regulation of the speed at which refractory material passes through chamber I0, and regulation of the rate at which sulfur and gas is charged to chamber 15.

Where the presence of steam in the reaction mixture is not objectionable, superheated steam at a temperature of approximately 900 F. may be charged through line i2 and used for purging instead of hydrocarbon gas.

The apparatus shown in Figure l is intended preferably for intermittent operations. Hot refractory material is intermittently charged to and withdrawn from chamber it] by operation of valves 3e and i6. Likewise, refractory material is intermittently withdrawn from receiver I! after exhausting gas therefrom by operation of valve 20.

Referring now to Figure 2, methane or other hydrocarbon gas or vapor enters through line 40,' passes through furnace 4| where it is preheated to a temperature:such that when mixed with sulfur the temperature of the mixture will be below the melting point of sulfur, then charged to aerating chamber 42 to which sulfur is fed through valve 43. The powdered sulfur becomes mixed with the gas from line 40 and the aerated mixture passes through line M to the top of vaporizing and superheating chamber 45. In chamber 35 the gas-sulfur mixture contacts a downwardly moving bed of hot refractory material whereupon the sulfur is immediately melted and vaporized and passes concurrently with the refractory material through the chamber 45. As it passes through the chamber, the sulfur is superheated to the desired temperature before it leaves the bottom portion thereof through line 46. Methane or other hydrocarbon gas or, when it is not objectionable, steam heated to approximately 900-950 F. in furnace 4| is charged through line 4'! into the bottom of chamber in order to purge the refractory material of any remaining sulfur. The gas charged through line 41 also acts as a seal to prevent sulfur vapors from passing out of the bottom of chamber 35. Chamber 45 is designed to function continuously at slightly above atmospheric pressure or at higher super-atmospheric pressure.

Powdered sulfur from hopper 48 passes either to hopper 49 or 50 at atmospheric pressure. While sulfur is being fed to one hopper, the other hopper is feeding sulfur to the aerating chamber 42. This is accomplished by closing valve 5| in the inlet to hopper 50 and the valve 52 in the outlet of hopper 49 and opening valve 53 in the inlet to hopper 49 and valve 54 in the outlet to hopper 50. Sulfur is then charged from hopper 48 through valve 53 under atmospheric pressure to hopper 49. At the same time powdered sulfur is caused to' flow from hopper 50 to aerating chamber 62 by pressuring hopper 50 through Valve-controlled line with methane or other gas similar to that charged through line 40.

; Sulfur is forced from hopper 50 through valve 54, line 56 and valve 43 to the aerating chamber 42 until hopper 50 is empty, at which time valve 54 is closed. During the time when sulfur is fed from hopper 5U, hopper 49 is filled with sulfur, valve 53 is closed and the hopper is pressured by means of gas forced into the top of the hopper through valve-controlled line 5?. The hopper is then ready to feed sulfur to the aerating chamber 42 as soon as hopper 56' is empty, by opening valve 52.

After valve 54 is closed, hopper 50 is depres- 'sured through valve controlled line 58after. which valve 215 I risoperied ahd :hopper 50 is. recharged with sulfur. Thealternate fillingand emptying of hoppers dfivan'd 'fill :is repeated in order to pro- -vide'for continuous flow'of sulfur to the aerating chamber llz. The gasremoved fromhoppers' lfl and -50 during the depressuring step maybe charged to line 40 for injection into the chamber 345.

In. order to provide forv continuous withdrawal J of refractory material from chamber IS, a dual hopper arrangement is connected tothe outlet of thechamber. While valve 59 intheoutlet of the chamber 45 and valve -60 inthe outlet of hopper6lare closed, valve 62 in the-inlet to hopper 6 I and valve 63 the outlet of hopper -64- are open. .1 Refractory material passes 5 from hopper 64 through line 65 to the bottomof elevator 66. During this time hopper 6| is filled with refractory material fromchamber -45 after "which valve--62 is closed and any-gas-which has passed *into the hopper 6i-with the refractory-material is removed throughvalve-controlled line-61. This gas may be-recycledtoeither line 46 or 67. When hopper --64 is empty, valve63 is closed and valve 59 is opened. Valve-60 is opened to permit reiractory materialto be discharged from hopper l6l to'elevator 66. Any gas accumulated in hopper 64 is eliminated through valve-controlled line lia-and this gas may be recycled to either line W or 41. Thereafter, valve 59 is open to permit hopperfi l to be again-charged withrefractory ma- -terialassoon as hopper His full. This alternate filling and emptying of hoppers 6| and fidis continued in order to make withdrawal of refractory material from chamber 45 continuous.

The refractory-material discharged from 'hopper Brand-64 is-picked -up 'by-eleVator66 and charged ---throug-h-line- 69 to the-top of kilnlfl. The elevator -66-- may be of the bucket or any other suitable type for transferring comminuted 'solid material.

The refractory "material moves downwardly through the kiln -as-acontinuous bed and is-heated therein by-means of a'mixture with air and combustiblematerial, either gas,

" liquidor powdered fuel, introduced through valvecontrolled lines "H and 12. The combustion or fiue gases are withdrawn from the kiln through valve-controlled lines-13, 'Hi'and75 and may, if

desired,--becirculateddn-whole or part through elevator-66 in orderto preheat the refractory material. Any gases passing upward through the elevator or through line fill are removed from the top of the elevator through valve-controlled A dual systemof hoppers is provided for discharging refractory material-from kiln wand recharging refractory material to 'chamber- 45.

Valves 1B and H are providedinthe inlets to 1 hoppers "l8 and I9 respectively, and valves 80 and is filled, valve' T! is closed and the. hopper 19 is pressured to a pressure equal to or slightly above that existing in chamber 45 by charging through valve-controlled line 82, gas similar to that charged through-line 4U. As'soon as hopper I8 is empty, valve8ll is closed and valve BI is opened 1 to permit refractory material to be charged from 'hopper 'l9 to the chamber 45. As soon as va-lve i 80 A is closed, hopper -18 i is depressured through valve-rcontrolled".line::84. 1 Gas taken zoif throug'h line 84 maybe recycled-to: chamber '45'z'through line-40 or may be'burned'in'kiln r10. Valve'16 is then opened andihot refractoryzmaterial :allowed to flowinto hopper 78. until filled, atzwhich time valve 16 is closed .and thehopperil'tlapressured by admitting through valve-controlled line 85 gas similar to that charged through line 140. This hopper is then ready; to feed refractorynmaterial to chamber 45'when'hopper79: is empty. When hopper l9 is'empty, valve-8| is; closed; the hopper is depressured through valve-controlled line 86 and is again ready to be'refilled. .Gas withdrawn through line BEmay berecycled to either line Bil-or to-kiln Ill. ,Thezcycl'e is repeated in order to continuously, feedhot refractory material from kiln 10 to chamber 45.

It will be apparent that the'aerated sulfur in Figure 2 may be fed to the lower portion. of reactor' 45 and the superheatedvsulfur vapors and hydrocarbons withdrawn from'the topthereof, as in-Figure 1. Likewise, it is apparent that the aerated sulfur in Figure 1 may be charged to the upper portion of chamber. 16 .and the superheated sulfur-vaporsand: hydrocarbons withdrawn from the lower portion: of .thechamber l0, asishown in Figure 2.

Referring now to Figure. 3; powdered refractory materialof about 100 meshsize orismaller, heated to the desired temperature, flows from hopper. 98 downwardly through vertical leg 9| and valve 92 and meetsa, stream of .preheated methane or othenhydrooarbon gas or vaporin .line '93. The methane or other gas or vapor. may-be preheated to any desired temperature, but preferablyi'to a temperature: approximating: the temperature of refractory. material. The methane'stream takes up the powdered refractory material in suspension and charges it into thebottomof the vaporizingand superheating chambered. Finely divided or powdered sulfur is'charged from: hopper .95 .downwardly through vertical leg '96 controlled by valve 9? and meets a stream of methane or other hydrocarbon gas. charged through line :93. The hydrocarbon charged through line 98 is preferably preheated to a'temperature which is insufiicient to melt the sulfur. jThe'sulfurhydrocarbon mixture is discharged into thelower portion of chamber 94 where it meets thevstream of hot refractory material and hydrocarbon.

. The sulfur is immediately melted "and .vaporized and passes upwardly through the chamber in concurrent relationship withthe hot r'efractorysmaterial and is superheated to the desired temperature. 'The sulfur vapor-hydrocarbonmixture and refractory material leave chamber-Q94 through-line 99 and pass into cyclone separator I00 .where the refractory material iss-eparated from the s'ulfur vapors and hydrocarbons. Refractory material :is withdrawn from separator iflllthrough line I!!! and fiows into hopper H32. Thesuper- 1 heated sulfur vapors and hydrocarbon gas leave the top of the cyclone separator through line I63. The powdered refractory material is withdrawn from hopper [02 through vertical leg [9 t controlled by valve H15 and passes to line we where it-meets astream of methane or other combustible gas charged to the line I06 at l Gland is carried in suspension into-the bottom of kiln Hi8. The carrier gas is preferably preheated prior to charging it at HJl. Ga similar to that introduced into the line 93- is introduced into leg m lthrough-valve-controlled line H39 to purge the refractory material leavingho-ppen H32 free of sulfur. The gas-introduced through-line- -l 09 is heated to a temperature above the vaporizing temperature of sulfur, preferably about 900- 950 F. The resulting sulfur vapors and gas escape from hopper 102 through line H and are returned through line 99 to separator I00.

Preheated air is admitted into the bottom of kiln I08 through valve-controlled line Ill in order to burn the gas admitted through 101. The refractory material carried in suspension in the gases undergoing combustion is heated to the desired temperature for vaporizing sulfur and superheating the vapors. A portion of the heat for heating the refractory material may be supplied by organic material deposited thereon during the vaporization of the sulfur. The hot refractory material and combustion flue gases leave the top of kiln I08 through line H2, pass into cyclone separator H3 where the refractory material is separated from the combustion gases. The refractory material passes through line H4 to hopper 90 and the combustion gases leave cyclone separator H3 through line H5. Methane or other gases which may be similar to that charged to line 93 is charged into line 9! through valve-controlled line HS in order to purge the refractory material in hopper 90 free of flue gas. The mixture of purging gas and flue gas is removed from hopper 90 through valve-controlled line H! and may be recycled to I01 or directly to kiln I08.

It will be understood that the apparatus shown and described in Figures 1, 2 and 3 will be made of or will be lined with refractory material, particularly those parts thereof which come in contact with sulfur vapors, thereby providing corrosion resistant equipment. This is made possible by virtue of the fact that vaporization and heating of the sulfur is accomplished by the hot refractory material which is cycled through the system. The refractory material used to make or line the apparatus which comes in contact with sulfur vapor may be of substantially the same type as the refractory material used for heating purposes.

As an example illustrating our process, a mixture of sulfur vapors and methane is prepared in which the mole ratio of sulfur and methane is approximately 1:1 for subsequent reaction in the presence of silica gel to form carbon disulfide. Granular Alundum, in the form of cylindrical pellets having a diameter of approximately of an inch and a length of approximately of an inch; is continuously circulated through the apparatus shown in Figure 1. In kiln 23 the Alundum pellets are heated by combustion of methane with air to a temperature of 1400" F. Methane is charged into the chamber 10 through line E5 and is preheated to a temperature of from '70 to 240 F. before contacting the sulfur. In chamber ill the mixture of methane and sulfur is vaporized and superheated to a temperature of 1200 F. under a pressure of 50 pounds per square inch gauge. The mixture of superheated sulfurmethane is charged from line H to a catalytic reactor for making carbon disulfide. Methane is charged through line 6 at a rate of 61.5 cubic feet per hour measured at 70 F. Sulfur is charged at the rate of 23.5 pounds per hour and the Alundum pellets are passed through chain-- her [0 at the rate of 1 cubic foot per hour. The temperature of the Alundum pellets leaving the bottom of the chamber 10 is approximately 900 F. Methane is used as purging gas and is charged through line I2 to-chamber It at a temperature of approximately 900950 F. Methane 75 terial in a separate 8 gas charged as purging gas through line 3| is heated to a temperature of approximatel 1400 F. prior to charging through line 29.

It will be seen, therefore, that wehave provided a method for preparing a mixture of sulfur vapors and hydrocarbon gas or vapor at appropriate temperature for reaction in a manner which avoids corrosion of the vaporizing and heating equipment and which obviates the necessity ofheating the reaction chamber so that a reaction chamber of refractory sulfur corrosion-resistant material can be used. It will also be seen that the mixture of sulfur vapor and hydrocarbon can be prepared at a pressure sufiicient to enable it to flow through a reaction system connected to the outlet of the vaporizing and superheating chamber.

In the appended claims it is to be understood that comminuted when employed as descriptive of the particle size of the refractory sulfur resistant heat transfer material connotes either a granular type particle size material which may be spherical, pelleted, extruded, etc. or a pulverulent or microspherical-type particle size material. Application of the correct description will depend upon whether the particular embodiment described in the applicable claim is directed to a fluidized process employing pulverulent type heat transfer agent, one form of which is schematically set forth in Figure 3, or a granular-particle moving bed type operation which is exemplified in Figure l and Figure 2 and which utilizes a less finely divided material than is employed in the aforementioned fluidized process. Both types of operation form specific embodiments of the instant application.

We claim:

1. The method of vaporizing sulfur comprising alternately heating comminuted refractory material, resistant to sulfur vapor corrosion, to temperatures above the boiling point of sulfur and bringing into contact with said heated material a suspension of powdered sulfur in a non-oxidizing hydrocarbon gas.

2. The method of vaporizing sulfur comprising circulating a comminuted solid refractory material, resistant to sulfur corrosion at temperatures above the boiling point of sulfur, through a heating zone and a vaporizing zone, heating said material to a temperature above the boiling point of sulfur in said heating zone, charging the heated material to said vaporizing zone, charging a suspension of sulfur in hydrocarbon gas to said vaporizing zone in direct contact with said heated material, maintaining the sulfur in contact with said heated material for a period of time suffcient to vaporize the sulfur, withdrawing sulfur vapors and gas from the vaporizing zone and recycling said material from the vaporizing zone to said heating zone.

3. The method of preparing a mixture of sulfur vapor and hydrocarbon for use in a subsequent reaction comprising charging a suspension of sulfur in hydrocarbon gas to a vaporizing zone resistant to sulfur corrosion, contacting said suspension in said vaporizing zone with comminuted refractory material heated to a temperature above the boiling point of sulfur for a period of time sufficient to vaporize the sulfur, withdrawing the mixed sulfur vapors and hydrocarbon gas from the vaporizing chamber, withdrawing the refractory material from the vaporizing zone before the temperature thereof falls below the boiling point of sulfur, heating the withdrawn refractory maheating zone to a temperature above the boiling point of sulfur and returning it to said vaporizing zone.

4. Method in accordance with claim 3 in which the comminuted refractory material is heated by direct contact with hot combustion gas.

5. Method in accordance with claim 3 in which the comminuted refractory material is heated by direct contact with hot combustion gas, the heated material is purged of combustion gas prior to contact with the sulfur and the refractory material is purged of sulfur prior to heating it with combustion gas.

6. Method in accordance with claim 3 in which the comminuted refractory material moves as a solid bed through the heating zone and the vaporizing zone.

7. Method in accordance with claim 3 in which the comminuted refractory material passes continuously as a solid bed through said heating zone and said vaporizing zone.

8. Method in accordance with claim 5 in which said comminuted refractory material passes through said heating and vaporizing zone in gaseous suspension.

9. The method of preparing a mixture of sulfur vapors and hydrocarbons at a temperature suitable for reaction in a separate reaction zone comprising circulating comminuted refractory material resistant to attack by sulfur vapors through a separate heating zone and a separate vaporizing zone resistant to sulfur vapor corrosion, heating said refractory material in said heating zone to a temperature substantially in excess of the boiling point of sulfur by direct contact with hot combustion gas, separating combustion gas from hot refractory material and charging the hot refractory material to said vaporizing zone while preventing combustion gas from entering said vaporizing zone, charging a suspension of powdered sulfur in gaseous hydrocarbon to said vaporizing zone in direct contact with said hot refractory material, providing suificient time of contact in said vaporizing zone to vaporize the sulfur, withdrawing vaporized sulfur and gaseous hydrocarbons from said vaporizing zone while preventing sulfur from entering said heater, withdrawing refractory material from said vaporizing zone before its temperature drops below the boiling point of sulfur, recycling the withdrawn refractory material to said heating zone and purging said refractory material of sulfur prior to recycling it to said heating zone.

10. Method in accordance with claim 9 in which the comminuted refractory material is charged to the vaporizing zone as a suspension in gaseous hydrocarbon preheated to approximately the temperature of the refractory material and the refractory material passes through the heating zone in the form of a gaseous suspension.

11. Method in accordance with claim 9 in which the comminuted refractory material is heated to a temperature of approximately 1400 F. in said heating zone and the sulfur-hydrocarbon mixture is heated to a temperature of approximately 1200 F. in said vaporizing zone.

12. The method of vaporizing sulfur compris ing, circulating a comminuted solid refractory material through a heating zone and a vaporizing zone, said refractory material being resistant to sulfur corrosion at temperatures above the boiling point of sulfur, heating said refractory material to a temperature above the boiling point of sulfur in said heating zone, charging said heated material to said vaporizing zone, charging a suspension of sulfur in a hydrocarbon gas to said vaporizing zone in direct contact with said heated material for a period of time suificient to vaporize the sulfur, withdrawing sulfur vapors and said hydrocarbon gas from the vaporizing zone, and recycling said refractory material from the vaporizing zone to said heating zone.

13. An apparatus for vaporizing sulfur comprising, a hopper for feeding solid comminuted sulfur to an aerating chamber, a heater for preheating a carrier gas, and conduit to conduct carrier gas from said heater to said aerating chamber wherein solid sulfur is mixed with said carrier gas, a vaporizer lined with refractory material resistant to high temperature sulfur vapor corrosion, a kiln for heating solid comminuted refractory material, means for circulating said solid comminuted refractory material from said kiln to said vaporizer and from said vaporizer back to said kiln, a conduit for carrying sulfur in said gaseous carrying medium from said aerating chamber to said vaporizer, means for withdrawing sulfur vapors from said vaporizer Without permitting said vapors to pass through said kiln, and means for purging said comminuted refractory material of adherent or occluded sulfur as it passes from said vaporizer, and means for separating sulfur from said purging gas and means for returning said sulfur to the sulfur feed.

14. An apparatus in accordance with claim 13 including means for suspending said comminuted refractory material in a gaseous medium before circulating it through said heater and said vaporizer.

MILTON M. MARISIC. CHARLES A. PORTER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,148,331 Olsson July 27, 1915 1,178,667 Niewerth Apr. 11, 1916 1,409,338 Fenton Mar. 14, 1922 1,638,992 Gillett Aug. 16, 1927 2,056,732 Mekler Oct. 6, 1936 2,239,801 Voorhees Apr. 29, 1941 2,320,318 Simpson et al May 25, 1943 2,331,433 Simpson et al Oct. 12, 1943 2,362,296 Murphree et al Nov. 7, 1944 2,392,289 McCullough et al. Jan. 1, 1946 2,446,388 Ramseyer Aug. 3, 1948 

1. THE METHOD OF VAPORIZING SULFUR COMPRISING ALTERNATELY HEATING COMMINUTED REFRACTORY MATERIAL, RESISTANT TO SULFUR VAPOR CORROSION, TO TEMPERATURES ABOVE THE BOILINGS POINT OF SULFUR AND BRINGING INTO CONTACT WITH SAID HEATED MATERIAL A SUSPENSION OF POWDERED SULFUR IN A NON-OXIDIZING HYDROCARBON GAS. 